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ZnO light-emitting devices with a lifetime of 6.

8hours
J. S. Liu, C. X. Shan, H. Shen, B. H. Li, Z. Z. Zhang, L. Liu, L. G. Zhang, and D. Z. Shen
Citation: Applied Physics Letters 101, 011106 (2012); doi: 10.1063/1.4733298
View online: http://dx.doi.org/10.1063/1.4733298
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APPLIED PHYSICS LETTERS 101, 011106 (2012)

ZnO light-emitting devices with a lifetime of 6.8 hours


J. S. Liu,1,2 C. X. Shan,1,a) H. Shen,1,2 B. H. Li,1 Z. Z. Zhang,1 L. Liu,1 L. G. Zhang,1
and D. Z. Shen1,a)

1
State Key Laboratory of Luminescence and Applications, Changchun Institute of Optics,
Fine Mechanics and Physics, Chinese Academy of Sciences, No.3888 Dongnanhu Road,
Changchun 130033, Peoples Republic of China
2
Graduate University of the Chinese Academy of Sciences, Beijing 100049, Peoples Republic of China

(Received 3 March 2012; accepted 19 June 2012; published online 5 July 2012)
Lithium-nitrogen doped p-type Mg0.25Zn0.75O films have been realized, and p-Mg0.25Zn0.75O/n-ZnO
single-heterostructured light-emitting devices (LEDs) have been constructed. Obvious emission
at around 392 nm has been observed from the LEDs under the injection of continuous current,
which can be attributed to the near-band-edge emission of ZnO. The LED can work continuously
for 6.8 h under a continuous current of 20 mA, revealing the good reliability of the LED.
The results reported in this letter reveal that reliable ZnO-based LEDs can be realized, thus
C 2012 American Institute of
high-performance ZnO-based LEDs may be promised in the future. V
Physics. [http://dx.doi.org/10.1063/1.4733298]

As a potential ultraviolet (UV) light-emitting material,


zinc oxide (ZnO) has received much attention in the past few
years. Besides its large bandgap (3.37 eV at room temperature), the most noteworthy property of ZnO lies in its large
exciton binding energy (60 meV), which is much larger than
the thermal energy at room temperature (about 26 meV).14
The above fact indicates that the excitonic effect of ZnO can
persist up to room temperature, and efficient excitonic UV
emission may be realized from ZnO. However, although
some ZnO light-emitting devices (LEDs) have been reported
in the past decades, the performance of the devices is still far
below expectation. Nitrogen has been regarded as one of the
most promising p-type dopant for ZnO,58 nevertheless,
some researchers have pointed out that p-type ZnO obtained
by employing nitrogen as a dopant is unstable, which means
that p-type ZnO will convert to n-type conduction after placing for a short period.9,10 The above facts cast a heavy
shadow over the realization of reliable ZnO LEDs. Lifetime
is one of the most important parameters of a LED, which
symbolizes the reliability of the devices. None report on the
lifetime of ZnO LEDs can be found up to now.
We have realized reproducible p-type ZnO films by
employing lithium (Li) and nitrogen (N) as a dual-acceptor
dopant in previous publication.11 In this letter, Li-N has been
employed as the dual-acceptor dopant for the p-type doping
of MgZnO, and p-MgZnO:(Li,N)/n-ZnO single heterostructures have been constructed. Obvious near-band-edge (NBE)
excitonic emissions coming from ZnO have been observed
from the structures at room temperature, and the devices can
work continuously for about 6.8 h in air ambient under the
injection of a continuous current of 20 mA, indicating the
good reliability of the LEDs.
The MgZnO/ZnO structures were grown on a-plane sapphire substrates in a VG V80H plasma-assisted molecular
beam epitaxy technique. The details for the growth of the
n-type ZnO can be found elsewhere.12 For the growth of the
a)

Authors to whom correspondence should be addressed. Electronic


addresses: shancx@ciomp.ac.cn and shendz@ciomp.ac.cn.

0003-6951/2012/101(1)/011106/4/$30.00

MgZnO:(Li,N) layers, elemental Zn, Li, and Mg contained


in individual Knudsen cells were employed as precursors, and
atomic oxygen and nitrogen generated from NO gas (6 N) via
a 13.56 MHz radio frequency plasma cell operated at 300 W
was employed as O and N source. During the growth process,
the pressure in the growth chamber was fixed at 2  105
mbar, and the substrate temperature at 700  C.
The electrical properties of the films were measured in a
Hall system (LakeShore 7707) under van der Pauw configuration. The morphology of the films was characterized by scanning electron microscopy (SEM) using a Hitachi S4800
microscope. A Bruker-D8 Discover x-ray diffractometer with
) radiation was used to evaluate the crystalCuKa (k 1.54 A
line properties of the films. Photoluminescence (PL) spectra of
the films were recorded employing the 325 nm line of a He-Cd
laser as the excitation source. The capacitance-voltage (C-V)
characteristics of the structures were measured by an Agilent
B1500A semiconductor analyzer. Electroluminescence (EL)
measurements were carried out in a Hitachi F4500 spectrometer under the drive of a continuous-current power source.
Figure 1(a) shows the x-ray diffraction (XRD) pattern of
the n-type ZnO film directly grown on a-plane sapphire.
Besides the diffraction from the sapphire substrate, only one
peak appears in the pattern, which can be indexed to the diffraction from (0002) facet of wurtzite ZnO. The strong (0002)
diffraction peak indicates that the ZnO films are crystallized
in wurtzite structure with c-axis preferred orientation. The
inset of Fig. 1(a) shows the x-ray rocking curve of the ZnO
films, which displays a symmetric Gaussian lineshape, and the
full width at half maximum (FWHM) of the curve is about
936 arcsec. Figure 1(b) illustrates the room temperature PL
spectrum of the ZnO film. The spectrum shows a dominant
NBE emission at around 380 nm with a FWHM of 11 nm. The
inset of Fig. 1(b) shows the SEM image of the n-type ZnO
film. The layer exhibits a smooth surface. The smooth surface
and acceptable crystalline quality of the n-ZnO layer lay a
solid ground for the following deposition of the MgZnO:
(Li,N) layer. The electron concentration of the n-ZnO film is
1.4  1019 cm3 and the mobility is 42 cm2/Vs.

101, 011106-1

C 2012 American Institute of Physics


V

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011106-2

Liu et al.

Appl. Phys. Lett. 101, 011106 (2012)

FIG. 2. (a) C-V characteristics of the Mg0.25Zn0.75O:(Li,N)/n-ZnO structure,


and the dependence of 1/C2 on the bias applied is also shown in the figure;
(b) Room temperature PL spectrum of the p-type Mg0.25Zn0.75O:(Li,N)
layer.

FIG. 1. (a) h2h XRD pattern of the n-ZnO film, and the inset shows the
(0002) x-ray rocking curve of the n-ZnO film; (b) Room temperature PL
spectrum of the n-ZnO film, and the inset shows the SEM image of the film.

A MgZnO:(Li,N) layer was deposited onto the n-ZnO


films to form the MgZnO:(Li,N)/n-ZnO structure. The
composition of the MgZnO determined by energy dispersive
x-ray spectroscopy is 25%. It is noted that the electrical properties of the Mg0.25Zn0.75O:(Li,N) film cannot been assessed
by direct Hall measurement because of the interference by
the underneath conductive n-ZnO layer. To characterize the
hole concentration of the Mg0.25Zn0.75O:(Li,N) layer, C-V
measurements on the Mg0.25Zn0.75O:(Li,N)/n-ZnO structure
was carried out, the results of which are shown in Fig. 2(a).
Considering the high electron concentration in the n-type ZnO
layer, the relationship of the capacitance and bias voltage can
be expressed by the following formula:13
1
2Vbi  V

;
2
C
qKs e0 NA2

(1)

where e0, Ks, q, N, A, and Vbi are permittivity of vacuum, relative dielectric constant, elementary charge, net acceptor concentration, junction area, and built-in potential, respectively.
The following expression can be deduced from Eq. (1)


2
1
:
(2)

N
qKs e0 A2
d1=C2 =dV
By inserting the known parameters into Eq. (2), and fitting
the dependence of the 1/C2 on the voltage applied, the net

acceptor concentration of the Mg0.25Zn0.75O:(Li,N) layer can


be deduced to be 5.5  1015 cm3. The formation mechanism
of Li,N doped p-type ZnO has been elucidated elsewhere,11,14 and Li substituted Zn (LiZn(Mg)) may act as
acceptor source, while the incorporated N may passivate the
interstitial Li to reduce the possible compensation to LiZn(Mg)
acceptors. The PL spectrum of the p-type Mg0.25Zn0.75O:
(Li,N) layer is shown in Fig. 2(b). One can see from the figure that a broad emission at around 340 nm superimposed by
several sharp peaks is visible. The sharp peaks are believed
to be the resonant Raman peaks of the Mg0.25Zn0.75O layer.
The schematic illustration of the p-Mg0.25Zn0.75O/
n-ZnO structure is shown in Fig. 3(a). The thickness of the
n-type ZnO and p-type Mg0.25Zn0.75O:(Li,N) layer is 600 nm
and 150 nm, respectively. Monolayer In and bilayer Ni/Au
electrodes were deposited in a thermal evaporation equipment as the n-type ZnO and the p-type Mg0.25Zn0.75O:(Li,N)
layer contacts. Note that the Ni/Au contact on the
p-Mg0.25Zn0.75O:(Li,N) layer was annealed at 400  C for
2 min to form ohmic contact. The current-voltage (I-V)
characteristics of the p-Mg0.25Zn0.75O:(Li,N)/n-ZnO structure exhibit a rectifying behavior with a turn-on voltage of
around 7.1 V, as shown in Fig. 3(b). The inset of Fig. 3(b)
shows that the I-V curves for both In contact on the n-ZnO
and Ni/Au contact on the p-Mg0.25Zn0.75O are nearly beelines, indicating that ohmic contacts have been formed. The
ohmic behaviors of the metal contacts excludes the possibility of the formation of any Schottky junctions in the device,
confirming that the rectification behavior arises from the
junction area. The relatively large leakage current may come

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011106-3

Liu et al.

FIG. 3. (a) Schematic illustration of the p-Mg0.25Zn0.75O:(Li,N)/n-ZnO


structure; (b) I-V characteristics of the structure, and the inset shows the I-V
curves of the Ni/Au contact on the p-type Mg0.25Zn0.75O layer and the In
contact on the n-type ZnO layer.

from the defects presented at the interface of the heterostructure that acts as parallel conduction pathways across the
LED.
Room temperature EL spectra of the structure are shown
in Fig. 4. The spectra are dominated by an emission at
around 392 nm, and another weak emission at around 500 nm
is also visible in the spectra. The emission at around 500 nm

FIG. 4. Room temperature EL spectra of the structure under different injection current, and the insets shows the dependence of the integrated emission
intensity of the band at around 392 nm on the injection current, in which the
scattered rectangles are experimental data, while the curve is the fitting
result.

Appl. Phys. Lett. 101, 011106 (2012)

has been frequently observed, and it can be attributed to the


deep-level related emission of ZnO.15,16 As for the emission
at around 392 nm, it can be attributed to the emission of the
n-ZnO layer. The output power of the devices is in the order
of tens of nanowatt. We note that the emission (392 nm)
shows slight redshift compared with the PL excitonic emission (380 nm) of ZnO. This discrepancy has been frequently
observed in semiconductors,17,18 and it might come from the
combination effect of the quantum confinement Stark effect
and the heating effect of the active layer of the devices.
Another phenomenon worth noting is that in the previously reported ZnO pn junctions, the EL emission is usually
located at around 420 nm,8,11,19,20 which has been attributed to
the donor-acceptor pair (DAP) emission from the p-type ZnO
layer.20 The appearance of DAP emissions in ZnO-based pn
junctions can be understood as follows: The mobility of
electrons is usually larger than that of holes, electrons in the
n-ZnO layer will enter into the p-ZnO layer, while few holes
in the p-ZnO layer can enter into the n-ZnO layer because of
their smaller mobility. Then electrons and holes will recombine in the p-type ZnO layer, in which there are many donorand acceptor-related levels. As a result, DAP emission
dominates the EL of the ZnO pn junction structured devices.
While the situation is different in our p-Mg0.25Zn0.75O:(Li,N)/
n-ZnO structures, in which the injection of electrons from the
n-type ZnO layer to the p-type Mg0.25Zn0.75O layer will be
blocked by the conduction band offset between these two
layers, while holes can drift from the p-type Mg0.25Zn0.75O
layer to the smaller bandgap n-type ZnO layer. As a result,
radiative recombination occurs in the ZnO layer, and the NBE
emission of ZnO has been observed.
The dependence of the integrated intensity of the emission at around 392 nm on the injection current is shown in
the inset of Fig. 4. One can see that the integrated intensity
increases superlinearly with the injection current. By fitting
the dependence curve using the following formula: INBE  Ik,
where INBE is the integrated intensity, I is the injection current, k is an index, the index of k can be derived to be 2.0 for
our case. This superlinear dependence suggests that the emission observed from the p-Mg0.25Zn0.75O:(Li,N)/n-ZnO structures may come from an excitonic emission.2123
Lifetime is one of the most important parameters of a
LED. To determine the lifetime of the p-Mg0.25Zn0.75O:
(Li,N)/n-ZnO structured LEDs, continuous current of 20 mA
was injected into the structure continuously, and the emission intensity of the structure was recorded intermittently.
Figure 5 shows the emission intensity of the band at 392 nm
as a function of the running time of the LED. A slight
increase in the emission intensity can be observed when the
running time is less than 1.4 h. After that the emission intensity decreases gradually. The slight increase has been
observed before,24 and it may come from the re-equalization
of the carriers in the active layer of the LEDs. One can see
from the curve that the LED can run continuously for around
6.8 h, and the spectrum of the device running after 6.8 h is
shown in the inset of Fig. 5. None report on the lifetime of a
ZnO-based LED has been demonstrated before. The above
fact reveals the good reliability of the ZnO LEDs, and confirms that the p-type MgZnO obtained by Li-N dual-acceptor
doping method is stable and reliable.

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011106-4

Liu et al.

Appl. Phys. Lett. 101, 011106 (2012)


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FIG. 5. The emission intensity of the p-Mg0.25Zn0.75O:(Li,N)/n-ZnO structured LED as a function of its running time, and the inset shows the EL spectrum of the device after running for 6.8 h.

In summary, p-Mg0.25Zn0.75O:(Li,N)/n-ZnO structured


LEDs have been constructed, and an emission at around
392 nm dominates the emission of the device, which can be
attributed to the NBE excitonic emission of ZnO. The device
can work continuously for 6.8 h under 20 mA continuous
current in air ambient. Although a lifetime of 6.8 h is still far
below from commercial demand, considering that none
report on the lifetime of ZnO-based LEDs can be found
before, the results reported in this letter reveal that reliable
ZnO LEDs can be realized, thus high-performance ZnObased LEDs may be promised in the future.
This work is supported by the National Basic Research
Program of China (2011CB302005), the Natural Science
Foundation of China (11074248, 11104265, and 61177040),
and the Science and Technology Developing Project of Jilin
Province (20111801).

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